Tionale de matiebes colobantes et manttfacttjbes de pbodtjits chimiqtjes



Patented Dec. 10, 1929 ANDRE 11mm: vrc'roa mm, -01 rams,

A PATENT OFFICE FRANCE, ASSIGNOB 'ro oouraen'm NA- TIONALE DE MITIERES COLORANTES ET MANUFACTURES DE PRODUITS CHIMIQUES DU NORD BEUNIES, ETABLISSEMENTS KUHLMANN, OF PARIS, FRANCE, A' CORZFO- RATI EON OF FRANCE ansmous CONDENSATION rnonuer Io Drawing. Application filed January 2, 1929, Serial 170. 829,941, and in France December 81, 1927.

The present invention relates to esters and new derivatives and their resinous condensationproducts obtained by combinatioirof an aliphatic polyhydric alcohol wlth a mlxture l of a polybasic acid and one or several natural resins (by the action of their resinic acids) and polymerization of the products formed.

Analogous products of condensatlon have now been obtained, starting from the known products, the saturated combinationor glynot or ingredients thereof. That is to say,

that glyceryl phthalate and a resinic ester are condensed together, or, what 1s equivalent, the ingredients of glyceryl hthalate may be added to resinic ester, pre ormed or otherwise, or the ingredients of resinic ester may be added to glyceryl phtha'late, preformed or otherwise.

In this specification, the terms polybasic acid and natural resins are to be construed in their widest sense and are specifically intended to include polybasic anhydrides in the one case and'and natural gums in the other.

Products analogous to those described above have been obtained as follows:

1. By condensing together a resinlc ester and a glyceryl plithalate, and heating progressively a mixture of thesetwo products, the following phenomenaare observed: Up to 200, there is a simple mixture and the product, treated by an ester, such as ethyl acetate, dissolves the resinic ester and leaves the insoluble glyceryl phthalate.

From 200 upwards, a gaseous emission with the formation of froth is observed, which is the si of a combination and the products obtaine on raising the temperature progressively, become entirely soluble in organic esters, such as ethyl acetate, and yield products of condensation analogous to but not identical with those described in the previous specifi. cation.

2. By adding either a mixture of one or sev- 'eral natural resins and glycerine to heated mass of g1 ceryl phthalate.

3. By a ding a mixture of phthalic anhydride and glycerine or phthalic anhydride only to a resinic ester alreadyformed or in the course of formation.

In a plication No. 329,939, the difi'erence was in icated between the construction of the base of the well-known glyptal resins and that of the new products.

The base of the new products was formed I from the three elements glycerine, phthalic acid and natural resin, all combined to produce an open-chain compound. To form the new resinous products this base waspolymerized, the result being a closed-ring or cyclic compound.

7 Now, in the present case, two groups of elements are employed, (1) glycerine and phthalic acid, (2) natural resin and glycerlne, and either group may be formed into a .rlng compound (i. e. polymerized) before combination with the other group. The number of different combinations of (1) with (2) is 4, but this includes the combinations torm-v ing the subject of application No. 329,939, so for the present invention the number is 3.

These combinations are indicated in the specioo oc o its where RCOOH represents the resinic acid,

which is clearly distinct from the bases'as I Example I A finely pulverized mixture of one-half glyceryl phthalate resin (Ubbelohde drop- P p t 1421l) entices-ha f resinic ter prepared from colophonyis V fused [at I 1'10-120.

, glycerine are added.

The temperature is pro essively raised.

From 200 n wards, an a undant gaseous emission is o served. The temperature is. raised up to 290 in 8hours, and the mass is oured when n been reached. The product obtained is entirely solublein the organic esters as-well as in their mixtures with alcohol and hydrocarbons. a

The product obtained has an Ubbelohde dr tipping point of 125130.

he proportion of glyceryl phthalate vvand resin used may be widely varied.-

Example [I maintained until complete fusion takes place and the temperature is raised to 260 in 4 hours. As soon as this temperature has been reached the mass is po red ofi. Theproduct obtained has an Ubb ohde dro ping point of 1 10-115 and is entirely solub e in organic not obtained having an esters, as well as in their mixtures with alcohol and hydrocarbons) E'wample II] To 200'grams of meltedcolophony are added, at 11012 0, 40 ams of glycerine, the

temperature '15 raise to 270280' in 2 hours and this temperature is maintained for 2' hours. 1 y

The temperature is allowed to decrease to about 200 and 200 grams of glycerine are added little by little, then the temperature is allowed to decrease to 110120, 285 grams of phthalic anhydride are added, the temperature is increased to 260 in 6 hours and then the mass is cured oft.

The pro not obtained has an Ubbelohde dropping point of 100-106 and is entirely soluble in organic esters as well as in the mixtures with alcohol and by hydrocarbons.

Example I V Into 200 grains of glycerine heated to 110 are introduced 285 grams of phthalic anhydride, and the temperature is increased to 170180 in 6 hours. A6180", 200 grams of finely pulverized Manillafgum (acidity 57.5 and 20 grams of glycerine are slowly adde The temperature 1s maintained at 180 until a homogeneous mass 'is obtained and this is heated to 260 in 4 hours.

The mass obtained is cured ofi, the prodlllbbelohde dropping pointof 112120 and is soluble in organic esters as well as in their mixtures with alcohol .and hydrocarbons.

are introduced; this temperature the temperature indicated has and the Congo gum is the period 0 Ewam/ple V Into 100 grams of melted colo hony are introduced, at 250, 100 grams 0 Congo gum, finely ground, and whilst maintaining the temperature at 250, 40 grams of glycerine is kept until a test yields a limpid globule. The resinic ester tgus obtained is poured ofl and is finely oun On the other hand, into 200 grams of glycerine are introduced 285 grams of phthalic anhydride, at 110, and the temperature is raised to 1701-80 in 6 hours. The ester previously prepared with the colophony then slowly added and the temperature is maintained until complete fusion takes place. The temperature is then 4 hours and cooling is unraised to 260 1n dertaken. The product obtained has an Ubbelohde dropping point of 1111 19'and' is soluble in organic esters as well as in their mixtures with alcohol and hydrocarbons.

The Ubbelohde dropping point as used in the above examples is the range of temperature between which a meniscus appears when a lump of resin is heated in a narrow vessel,

and a drop is formed which falls frol'maperforation in the bottom of the vessel. The apparatus of Ubbelohde is explained'and described in the work of Hans Wolfi' (Berlin), translated into French as Manuel de Laboratoire- Pour LIndustrie des Vernis et Couleurs, by Jowe, published in Paris by Charles Beganger in 1926. Reference is to pages 7 an 8. a

' The above examples are not limited as concerns the proportions, processes, periodand temperature of heating and nature of the resin or natural resins orgums employed. It is in fact possible tosubstitute for or the other, colophony, Congo gum, Manilla gum, dammar gum etc. The dropping points are likewise variable, within quite wide limits, with the roportions of the constituents, heating and the temperature reached, that is to say, with the degree of polymerization.

These new resins, with regard to solvents, are easily dissolved in esters, such as ethyl acetate, butyl acetate, amylacetate, benzyl acetate, ethyl phthalate, butyl phthalate, amyl phthalate, etc. In mixed solvents the new products also have a. very high solubility, clearly better than that of most of the known synthetic resins, which gives them a new technical quality and a special aptitude for entering into the preparation of industrial products for example, for the preparation of varnishes, lacquer paints, nitro-cellulose and aceto-cellulose varnishes, either alone or in combination with natural gums, nitrocellulose, aceto-cellulose, mineral or organic pigments or. any other ingredients.' s

n the same way, they can be adap ed to ganic esters, the product having tusibility v alcohol with a polybasic acid in proportions such as-"to combine substantially all of the hydroxyl groups of the alcohol, and a natural resin and a polyhydric alcohol in proportions such as to form a resinic ester, said ingredients being condensed together to form a product which is entirely soluble in orindicated. by an Ubbelohde dropping point between approximately 100 and 135 G.

2. A new resinous condensation product, comprising a combination of an ester formed by condensation of a polybasic acidic compound and a polyhydric alcohol in proportions such as to-combine substantially all the hydroxyl groups of the alcohol with a resinic ester formed by combining a natural resin with a polyhydric alcohol.

1 3. Product as defined in claim'2, wherein the polybasic acidic substance employed is 1 phthalic anhydride.

4 Product as defined in claim 2, wherein the polyhydric alcohol employed to form each ester is glycerineQ 5. Ainew resinous condensation product, comprising a combination of an ester formed by condensation of a poly'basic acidic com- 4 pound and a polyhydric alcohol in propor- 'tions such as to combine substantially all the hydroxyl grougsof the alcohol with a resinic ester formed y combining a natural resin with a polyhydric alcohol, and compounded with a siccative oil.

In testimony whereof I have, hereunto affixed my signature.

ANDRE HENRI VICTOR DURB. 

